Reaction products of pyrophosphoric acid with acyl derivatives of polyhydroxy substances



Patented Oct. 31, 1939 UNI ED STATES REACTION PRODUCTS OF PYBOPHOSPHOB- 1G ACID WITH ACYL DERIVATIVES F POLYHYDROXY SUBSTANCES Benjamin B. Harris, Chicago, II].

No Drawing. Application October 1'1, 1938, Serial No. 106,194

17 Claims.

My invention relates to a new class of chemical substances. It relates more in particular to a class of chemical substances having the properties of interface modifiers when employed in a treating bath containing textile, leather or ores. Many of the compounds of my invention are also effective to decrease the spattering of margarine, to increase the oiliness of lubricating oils and greases, such as are derived from mineral oils, and are also useful in retarding the rancidification of oils, fats, and vitamin preparations which are subject to deterioration by oxidation.

The object of the invention is the provision of a new class of chemical substances.

Another object is the provision of a class of chemical substances adapted for use as interface modifiers.

The substances of my invention have many useful applications in the arts where frothing, wetting, penetrating, detergent, emulsifying, and other interface modifying functions are required. They are in general possessed of at least three groups, one having a hydrophile function, another having a lipophile function in the molecule, and the third group forming a link between the hydrophile and lipophile groups. The hydrophile function is performed primarily by a pyrophosphoric acid group, giving the molecule as a whole an afiinity for aqueous materials. The lipophile group is any radical such as acyl or alkyl derived from a fatty acid or its corresponding alcohol and has a definite afllnity for ofls and fats. The hydrophile pyrophosphoric acid group is linked to the lipophile group by means of a polyhydroxy substance. I have found polyhydroxy substances such as sugars, sugar alcohols, glycols, polyglycols, glycerol, polyglycerols, and hydroxycarboxylic acids to be particularly suitable. The linkage between the polyhydroxy substance and the lipophile group may be either an ester or ether linkage.

More specifically, the most preferable of the compounds of my invention may be defined as reaction products of pyrophosphoric acid with polyhydroxy substances wherein at least one hydroxy group of the polyhydroxy substance has its hydrogen substituted by a lipophile group. The lipophile group may include any organic acid group, particularly fatty acid groups having preferably at least four carbon atoms such as the fatty acid radicals of the following acids: caproic acid, capric, caprylic, valeric, butyric, abietic, naphthenic, hydroxystearic, benzoic, benzoylbenzoic, naphthoic, toluic, higher molecular weight saturated and unsaturated fatty acids including palmitic acid, stearic, lauric, melissic, oleic, myristic, rlcinoleic, linoleic acid or mixed fatty acids derived from animal or vegetable fats and fish oils such as lard, oleo oil, coconut oil, corn oil, cottonseed oil, partially or completely hydrogenated vegetable oils such as cottonseed oil, corn oil, sesame oil and fatty acids of various'waxes such as beeswax and camauba wax; or the lipophile group may be an alkyl radical derived from an alcohol corresponding to any of the preceding acids, such as octanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, lauryl alcohol, higher saturated and unsaturated aliphatic alcohols derived from natural fats and oils, cholesterol, sperm oil, etc.

Specific examples of polyhydroxy substances, the residues of which may serve as linkages between the lipophile groups and the hydrophi le pyrophosphoric acid groups, besides those previously mentioned, are as follows: mucic acid, tartaric acid, saccharic acid, gluconic acid, glucuronic' acid, gulonic acid, mannonic acid, trihydroxyglutaric acid, glyceric acid, and the like, as well as carboxylic oxidation products of polyglycerols which may be represented by the formulae:

tn. tn.

11-41-011 n-e-on o=eon ale-on 0 on on o no-aen-cmo-cm-entt-on 0 on on on o ao-e-en-cHro-cm-en-crrro-cnren-ti-on 0 on r on o from 250 C. to 260 C. for about three hours in the presence of an inert gas. This reaction mixture will give a mixture of various polyglycerols, the size of the molecules depending upon the time of polymerization. The mixture of polyglycerols is then oxidized with mild oxidizing agents to convert at least one of the primary hydroxy groups to a carboxylic group.

Examples of substances of my invention are as follows:

1. The reaction product of pyrophosphoric acid with mono-olein, ammonium salt.

2. The reaction product of pyrophosphoric acid with di-olein, triethanolamine salt.

3. The reaction product of pyrophosphoric acid with mono-laurin, sodium salt.

4. The reaction product of pyrophosphoric acid with nrono-acetin, sodium salt.

5. The reaction product of pyrophosphoric acid with di-butyrin, sodium salt.

6. The reaction product of pyrophosphoric acid with cetyl ether of sorbitol.

7. The reaction product of pyrophosphoric acid with ethylene glycol mono-stearate.

8. The reaction product of pyrophosphoric acid with ethyl ether of ethylene glycol.

9. The reaction product of pyrophosphoric acid with octanoic acid ester of diethylene glycol.

10. The reaction product of pyrophosphoric acid with mixed coconut oil fatty acid ester of diethylene glycol, ammonium salt.

11. The reaction product of pyrophosphoric acid with butyl ether of diethylene glycol, sodium salt.

12. The reaction product of pyrophosphoric acid with sucrose mono-oleate, sodium salt.

13. The reaction product of pyrophosphoric acid with mixed cocoanut oil fatty acid monoor diglycerides or mixtures of monoand diglycerides, ammonium or triethanolamine salts.

14. The reaction product of two mols of pyrophosphoric acid with one mol of sucrose distearate, ammonium salt.

15. The reaction product of pyrophosphoric acid with mono-oleic acid ester of diglycerol, sodium salt.

16. The reaction product of pyrophosphoric acid with mono-octyl ether of glycerol, potassium salt.

17. The reaction product of pyrophosphoric acid with di-caproin, sodium salt.

18. The reaction product of two mols of pyrophosphoric acid with one mol of mono-cetyl' glycerol, potassium salt.

19. The reaction product of pyrophosphoric acid with lauryl ether of diethylene glycol, sodium salt.

20. The reaction product of pyrophosphoric acid with mono-melissic acid ester of mannitol, ammonium salt.

21. The reaction product of pyrophosphoric acid with di-cetyl ether of sorbitol, monoethanolamine salt.

22. The reaction product of pyrophosphoric acid with di-stearic acid ester of triglycerol, potassium salt.

23. The reaction product of pyrophosphoric acid with mono-butyric acid ester of tartaric acid.

24. The reaction product of pyrophosphoric acid with mono-propionic acid ester of mucic acid, sodium salt.

25. The reaction product of pyrophosphoric acid with monoabietic acid ester of glycerol, ammonium salt.

26. The reaction product of pyrophosphoric acid with mono-benzoic acid ester of glycerol, sodium salt.

27. The reaction product of pyrophosphoric acid with di-oleic acid ester 01 diethylene glycol.

There are several methods by means of which the materials of my invention may be made. The method employed should be determined primarily by considering the type of substance to be produced. In introducing the pyrophosphoric acid radical, for example, a material containingan esteriflable hydroxy group is reacted with pyrophosphoric acid. Either one or more pyrophosphoric acid radicals may be introduced, depending upon the substance desired. A condensing agent and/or a solvent may be added where required.

Example I Approximately 25 parts of the coconut oil mono fatty acid ester of ethylene glycol is poured into about 54 parts of pyrophosphoric acid and the two are mixed together until homogeneous. When the temperature has ceased rising, the mass is heated to 90 degrees C. with stirring. If no further temperature rise is noted, the mass is permitted to cool and is then extracted with ether. The ether extract may be neutralized by passinginto the same a gaseous stream of ammonia until a definite color change is noted. The ether is then evaporated.

In place of the coconut oil mono-fatty acid ester of ethylene glycol, I may use the coconut oil mono-fatty acid ester of diethylene glycol.

Example II Approximately 77, parts of mono stearin (washed and dried) is heated to 90 degrees C. and is added to about 18 parts of pyrophosphoric acid also heated to the same temperature and the two are mixed until a homogeneous mass is obtained. The mass is stirred continuously until the heat of reaction ceases after which the mass is extracted with ether and neutralized and the ether evaporated in the same way as shown in Example I hereinabove.

Example III To 115 grams of pyrophosphoric acid at 90 degrees C. there is added with stirring 71 parts of mono stearin at 85 degrees C. The temperature of the mass rises to approximately 110 to 115 degrees C. after which it is allowed to cool. The resulting solid mass is mixed with a cold solution of 80 grams of sodium hydroxide dissolved in 400 cc. of water and the mixture is well stirred until all of the acid is neutralized. The solution is kept cold by means of an ice bath and also by addingsmall amounts of ice to the mixture. The resulting product is a thin paste comprising the sodium salt of the reaction product of pyrophosphoric acid with mono stearin and contains, in addition, the inorganic sodium salt oi pyrophosphoric acid.

Example IV A mixture of 641 parts of myristic acid and 700 parts of glycerine is heated in an atmosphere of carbon dioxide at about 220 degrees C. for 2 hours, the moisture formed being permitted to escape. Upon cooling, 9. yield of 900 parts of mono myristin is obtained. parts of the mono myristin is washed three times with water at 90 degrees C. and is dried by dissolving the washed substance in ether and adding enough anhydrous sodium sulphate to take up all of the moisture. The ether extract is then filtered and slightly evaporated. A crystalline substance comes out of the ether solution, the mass is filtered and is then thoroughly dried. Into 17 parts of pyrophosphoric acid at degrees 0. there are stirred 10 parts of the crystallized mono myristin at 90 degrees C. whereupon the temperature rises to approximately degrees C. The mixture is then heated to degrees C. for about 10 minutes and is then allowed to cool. The resulting solid massis then extracted with ether, the extract is centrifuged and filtered and is then neutralized with a stream of gaseous ammonia. A white precipitate comes down which is filtered ofi and is then thoroughly dried. The resulting product is a white somewhat plastic solid.

Example V A mixture of 2 and parts of cottonseed oil, 2 and A; parts of hydrogenated cottonseed oil having an iodin value of 68 to 70, and 5 parts of glycerin are heated to a temperature of 250 to 260 degrees C(for 2 hours using 0.005 part of sodium hydroxide as a catalyst. The reaction mixture is heated in a non-oxidizing atmosphere, such as carbon dioxide, and is continuously stirred in any suitable way during the entire reaction. After the completion of the reaction, the mass is permitted to stand and the excess glycerin, which constitutes the bottom layer, is drawn ofi from the desired monoglycerides which comprise the top layer.

To 36 parts of pyrophosphoric acid at room temperature (30 degrees C.) is added 77 parts of the above described mono glyceride at room temperature (30 degrees C.). The two components are then well mixed and the temperature rises to approximately 55 degrees C. The reacting.

mass is then mixed for about 30 minutes longer until the temperature thereof drops back to approximately 30 degrees C. The resulting product is a light brown plastic material. This is allowed to stand for about 15 hours and is then transferred to a mortar to which is slowly added 24 parts of sodium hydroxide dissolved in 90 parts of water. During the entire neutralization, the mass is kept at a temperature between 5 and 10 degrees C. with powdered dry ice. Upon each addition of alkali, the mass is intimately mixed. The final product is a cream colored somewhat limpid paste and comprises the sodium salts of the reactionproduct of pyrophosphoric acid with the mono-glycerides of the fatty acids present in the cottonseed oil.

While all of the substances of my invention fall into the category of interface modifiers, they modify an interface in various ways and to various extents, depending upon the relative potencles of the hydrophile and lipophile groups, the resultant of the two representing the interfacial function of the molecule as a whole.

While the illustrative examples listed hereinabove represent in some cases single substances,

.low and then react. this mixture of diglycerides with pyrophosphoric acid. In place of pure monostearin, I may use a commercial product which contains small proportions of monopalmitin and mono-olein, or small proportions of the di-fatty acid esters of glycerin.

In general, in place of extracting the pyrophosphoric acid reaction product with a solvent such as ether or other organic solvent, the pyrophosphoric acid reaction product may be salted out by dispersing it in water, then adding salt and then collecting the ester which separates out.

It is evident that I may prepare the ethers or the esters of the polyhydroxy-substances in any desired or known ways and subsequently one mol thereof with one or more mols of pyrophosphoric acid or, alternatively, I may first react the polyhydroxy substance with pyrophosphoric acid and I may then esterify or etherify one or more of the remaining. hydroxy groups of the polyhydroxy substance by esterifying or etherifying procedures well known in the art.

The polyhydroxy substances which are the linking substances between the lipophile. group or groups and the hydrophile pyrophosphoric acid group may be conveniently considered as falling into two groups. The first of these groups includes compounds containing less than four esterifiable hydroxy groups and is exemplified by glycerine, glycol and polyglycols. The second group contains those substances which have more than three esterifiable hydroxy groups, examples of which are the sugars and sugar alcohols, the polyglycerols such as diand tri-glycerol, etc. It will be-understood that my compounds may have one or more lipophile radicals and one or more hydrophile pyrophosphoric acid radicals attached to the polyhydroxy substance. Thus, for example, I may react one mol of pyrophosphoric acid with one mol of the dioleic acid ester of sucrose, or two mols of pyrophosphoric acid with one mol of the dioleic acid ester of sucrose. Similarly, I may react one mol of the di-stearic or other fatty acid ester of dior tri-glycerol with either one or two mols of pyrophosphoric acid. In a similar way, as described above, instead of the acyl derivatives of the polyhydroxy substances I produce the corresponding alkyl derivatives.

As I have described above, my compounds may contain either ester or ether linkages. Any known methods of etherifying polyhydroxy substances may be employed. The following examples are illustrative:

Erample.Sodium octylate is treated with a 25% molal excess of glycerine is reacted withv excess ethylene glycol chlorhydrin by the procedure described in the above example to form the glycol mono cetyl ether. This is then treated with pyrophosphoric acid. This reaction product may be neutralized with ammonia or some other alkaline or potentially alkaline material to give salts thereof.

The following chart represents further details of my invention and is self-explanatory:

. nary ammonium bases, and also other anti-acid materials in which case hydrogen of the pyro- M013 Mols Mols orv Expe" of subpyrophospympl-ws' Type Solubility of Appearance of 52: Name Substanw used stance phoric gg of salt salt in water compound i acid unreected Diolein 1 3 1. NHA- Boluble Amber colored mass. Mixed mono-coconut fatty acid esters of 1 3 1.2 NH4 d Cream colored nearly ethylene glycol (washed and dried). solid paste. i -f i 3 5' t. d?" lift? it? it.

85 01' O1 4-- g a I I.-

like mass. Mono-stearie acid ester of polyglycerols 1 8 0.0 NH| Light brownsolid M(moLtwt. 610). 1 3 2 2 NH (pow ersl. ed Id one s Parin 4-- ream 00 or so i I I (P wders Tr1-at %0 acidesters oi polyglycerols (mol. l 3 0.0 N H Insoluble Reddish brown pasty w so Distearin 1 3 1. 8 NH sligl tly 301- Light brown solid.

u e. Diolein 2 1 0.0 NH4- Insoluble Brownish red oil. Mono stearin (washed and dried) 2 l 0. 4 N H4- Dispierses bult 0128;)!!! d colored solid no verysow are uble. Mixed mono-coconut fatty acid esters of 2 1 0. 14 NH Solublc.-. Deep cream colored ethylene glycol (washed and dried). still. paste. Mono myristin (pure) 3 1. 7 N114.- d0...... Wthite iaamewhet plasic so i While mypreferred compounds are reaction products of pyrophosphoric acid with polyhydroxy substances wherein at least one hydroxy group of the polyhydroxy substance is esterified or etherified with a group containing at least four carbon atoms, and more desirably at least eight carbon atoms, still, for some purposes, the last mentioned group may contain less than four carbon atoms as, for example, in the case of the reaction product of pyrophosphoric acid with mono-acetin (sodium salt), number 4 in the list of compounds mentioned above. The propionic acid and such lower fatty acids may be employed in partially esterifying the polyhydroxy substance which may then be reacted with pyrophosphoric acid.

It is within the broad confines of my invention, however, to produce other types of compounds containing a pyrophosphoric acid group. For example, in tri-olein, the pyrophosphoric acid radical apparently adds on to the double bond of the oleic acid portion of the molecule. Other compounds of the same character which react to add pyrophosphoric acid at a double bond are mono-olein di-stearate, olive oil, cocoa butter,-

lard, etc.

Other compounds of which reaction products with pyrophosphoric-acid may be made are higher molecular weight hydroxy-carboxylic acids. Examples of such acids are ricinoleic acid, di-hydroxy stearic acid prepared by hydroxylation of oleic acid, and tri-hydroxy stearic acid prepared by hydroxylation of ricinoleic acid.

In the neutralization of the pyrophophoric acid group or groups, considerable latitude and modification may be employed. While said group or groups may be left unneutralized, I find that, in general, the products are more suited to the purpose for which they are intended if they are treated with a suitable inorganic or organic antiacid agent to form the neutral or acid salt. Examples of inorganic and organic anti-acid agents which may be used satisfactorily are bicarbonates of the alkali metals, potassium hydroxide, potassium carbonate, metallic sodium, sodium hydroxide, sodium oxide, sodium carbonate, ammonium hydroxide ammonia gas, and other anti-acid materials of the alkali earth group,sodium stearate, calcium stearate, aliphatic and aromatic amines, alkylolamines, such as mono-, diand tri-ethanolamine and mixtures thereof, quaterphosphoric acid group or groups is replaced by a. cation such as sodium, potassium, ammonium, calcium, magnesium, aluminum, zinc, amines, alkylolamines, etc. It will be understood that by the term "cation, as used throughout the specification and claims is meant such elements as are mentioned herein and, in general, atoms or radicals which are regarded as hearing a positive charge. The pyrophosphoric acid reaction products may be neutralized to methyl orange, litmus, or phenolphthalein.

The products above described may be added in suitable proportions to a treating bath containing an aqueous medium, with or without an additional substance, such as for example alkalis, mordants, dyes, color discharging reagents, H202, color reducing agents, oils, sulphonated oils, mordanting salts, fabrics and other reagents or substances used in treating baths, and the treating bath.so formed ,can be employed with satisfaction in all of thearts in which interface modification is desired. For example, dyeing, bleaching, scouring, leather stuffing, and otherwise treating fabrics, fibers and other materials in a treating bath of this character is productive of good results. Also in the stufling of leather, dyeing, and otherwise treating, furs, and in many other arts, a treating bath employing the materials of my invention maybe used. In flotation of ores it may be used by itself orin connection with other reagents such as oieaginous agents of vegetable or mineral origin, collecting agents such as fatty acids, depressants, etc. to modify the interface between the finely divided ore and the aqueous medium.

While I have described several methods for the preparation of the materials of my invention, it must be understood that the scope of the invented class of substances is by no means limited by these methods. Other convenient methods may be used. This also applies, and particularly so, to supplementary procedures of purification or isolation which lie strictly within the province of skill of any qualified chemist whose procedures in each instance must begoverned by the properties of the materials concerned, and by the degree or the character of the purity desired.

It will be appreciated that it is unnecessary to employ pure pyrophosphoric acid in producing the reaction products of my invention. Good results were obtained using an acid containing approximately 80% pyrophosphoric acid, a small amount of meta-phosphoric acid, and a very slight amount of ortho-phosphoric acid.

Wherever the prefix poly is employed, it will be understood to mean more than one.

The term residue, as used throughout the specification and claims, is employed in its ordinarily understood chemical significance. For example, where one of the hydroxyl groups of glycerine is esterified with a fatty acid or etherified with an alcohol and one mol of said compound is reacted with one mol of pyrophosphoric acid, that which remains of the glycerine molecule, for example CHOH is the residue of the polyhydroxy substance, in this case glycerine.

Whenever the term reaction product of pyrophosphoric acid is employed in the claims, it will be understood to cover the reaction product as such or neutralized in whole or in part by a suitable base as described, unless otherwise qualified.

What I claim as new and desire to protect by Letters Patent of the United States is:

1. A reaction product of pyrophosphoric acid with an aliphatic polyhydroxy substance containing at least one free hydroxy group and wherein the hydrogen of at least one other hydroxy group of the aliphatic polyhydroxy substance is replaced by an organic carboxylic acyl radical.

2. A reaction product of pyrophosphoric acid with an aliphatic polyhydroxy substance containing at least one free hydroxy group and wherein the hydrogen of at least one other hydroxy group of the aliphatic polyhydroxy substance is replaced by an organic carboxylic acyl radical containing at least four carbon atoms.

3. A reaction product of pyrophosphoric acid with an aliphatic polyhydroxy substance containing at least one free hydroxy group and wherein the hydrogen of at least one other hydroxy group oi the aliphatic polyhydroxy substance is replaced by an organic carboxylic acyl radical, said polyhydroxy substance being a member of the group consisting of glycerol, glycols, polyglycerols, polyglycols, sugars, sugar alcohols, and hydroxycarboxylic acids.

4. A reaction product of pyrophosphoric acid with an aliphatic polyhydroxy substance wherein the hydrogen of at least one hydroxy group of the aliphatic polyhydroxy substance is replaced by an organic unsaturated carboxylic acyl radical containing at least four carbon atoms, said polyhydroxy substance being a member of the group consisting of glycerol, glycols, polyglycerols, pvly lycols, sugars, sugar alcohols, and hydroxycarboxylic acids.

5. A reaction product of pyrophosphoric acid with an aliphatic polyhydric alcohol wherein at least one hydroxy group of the alcohol has its hydrogen replaced by an organic carboxy 8 group containing at least four carbon atoms and at least one double bond.

6. A reaction product of pyrophosphoric acid with an aliphatic polyhydric alcohol wherein at least one hydroxy group of the alcohol is esterified by a fatty acid containing at least one double bond and at least four but less than eighteen carbon atoms.

7. A reaction product of pyrophosphoric acid with a fatty acid monoglyceride, the fatty acid radical containing at least four carbon atoms.

" 8. A reaction product of pyrophosphoric acid with a fatty acid monoglyceride.

9. A reaction product of pyrophosphoric acid with a higher fatty acid glyceride containing at least one unsaturated higher fatty acid acyl radical.

10. A reaction product of pyrophosphoric acid with an aliphatic dihydroxy substance, where the hydrogen of one hydroxy group is replaced by an organic carboxylic acyl radical containing at least four carbon atoms.

11. A reaction product of pyrophosphoric acid with an aliphatic polyhydroxy substance with at least four carbon atoms and with at least two esterifiable hydroxy groups, wherein the hydrogen of one hydroxy group is replaced by an organic carboxylic acyl radical which contains at least four carbon atoms. v

12. A reaction product of pyrophosphoric acid with an aliphatic polyhydroxy substance having not less than four esterifiable hydroxy groups, the hydrogen of at least one hydroxy group being replaced by an organic carboxylic acyl radical, the aliphatic polyhydroxy substance containing at least one free hydroxy group available for reaction with the pyrophosphoric acid.

13. A reaction product of at least two mols of pyrophosphoric acid with one mol of an aliphatic polyhydroxy substance, the hydrogen of at least one of said hydroxy groups being replaced by an organic carboxylic acyl radical, the aliphatic polyhydroxy substance containing at least two free hydroxy groups available for reaction with the pyrophosphoric acid.

14. A reaction product of pyrophosphoric acid with a polyglycerol, the hydrogen of at least one hydroxy group of the polyglycerol being replaced by an organic carboxylic acyl radical, the polyglycerol containing at least one free hydroxy group available for reaction with the pyrophosphoric acid.

15. Reaction products of pyrophosphoric acid with mixed cocoanut oil mono-fatty acid esters of a glycol.

16. Reaction products of pyrophosphoric acid with mixed cocoanut oil mono-fatty acid esters of diethylene glycol.

17. A reaction product of pyrophosphoric acid with an aliphatic polyhydroxy substance wherein the aliphatic polyhydroxy substance has only one hydroxy group in which the hydrogen has been replaced by an organic carboxylic acyl group containing at least four carbon atoms.

. BENJAMIN R. HARRIS. 

